Cembinder

A particular technology

Cembinder Functions in Hydraulic Binders

Stabilizing - Bleed and segregation Accelerating - Set accelerator - Early strength enhancer

Colloidal Silica in use

What is Colloidal Silica?

Definition of a Colloid

Small insoluble, non-diffusable particles, larger than molecules but small enough to remain suspended in a fluid medium without settling

Cembinder W50
OH Si

5 nm (10-9m)

O Si O O Si OH

Na Water

Anionic particles in water pH > 8 Sodium stabilized

OH O Si O O O Al OH O O Si OH O Al O Si O Si O O Si O Al O

Water

Si

Cl Surface area of one gram = 500 m2 Water

more than 10 000 000 000 000 000 000 (1019) particles per gram

Characteristics of Cembinder
Anionic particles pH 8 11 Sizes from 2 100 nm SiO2- concentration 8 50% Sodium stabilized < 1% as (Na20) Hydrophilic behavior Low viscosity Water as the fluid No other chemicals added Not toxic GREEN on the PLONOR list Shelf life 12 months, when stored in 5 - 35C

OH Si O Si OO Si OH

Na+ Water

The four basic Colloidal Silica grades

OH Si O Si O Si OH OH O Si O O O Al O

Si

R
O Si OO Si

O Si

OH

Al O O Si O Si O

O Si OH

Si O O

Al

Standard
pH > 8 Anionic particles Sodium or ammonia stabilized

Surface-modified
pH 4-9 Anionic particles High surface charge

Organo-modified
pH 7-9 Anionic particles, reduced number of charged groups Steric stabilized by an organic chain, R

Surface coated
pH < 5 Cationic particles Chloride stabilized

Maximum Silica Concentration vs. Particle Diameter

60

Unstable Region
40 SiO2 (%)

Stable Region
20

0 0 10 20 30 40 50 60 70 80 90 100 Particle Diameter (nm)

Characteristics of Cembinder grades

CEMBINDER physical properties

CB W50 SiO2 (%) Average Particle size (nm) [Surface Area (m2/g)] Density (g/ccm) pH Viscosity (cP) Manufacturing plant 15 5 [500] 1.1 10.0 <10 All CB W25 30 11 [250] 1.2 10.4 <12 All except Sweden CB W8 50 32 [85] 1.4 9.5 <15 Sweden, USA and Taiwan CB W75 15 3.5 [750] 1.1 10.5 <15 All

Three Types of Synthetic Amorphous* Silica

Silica Fume hard aggregates

Precipitated silica

grape clusters

Colloidal silica

primary particles

* amorphous \J-mor-fJs\ adj [Gk amorphos, fr. a- + morphs form] (ca. 1731): 1a: having no definite form; shapeless: as b: lacking complex bodily organization c: lacking division into parts d: uncrystallized

Physical Characteristics of Synthetic Amorphous Silicas

Type Density Aggregate Size Primary Particle Surface Area Appearance

Silica Fume

2.2 g/cc

1 m

2-100 nm

~80 m2/g

Dry powder

Precipitated Silica

10 lbs/ft3 (0.16 g/cc) ~72 lbs/ft3 (1.15 g/cc)

1-5 m

20-50 nm

20-100 m2/g

Dry powder

Colloidal Silica

n/a

5-150 nm

50-800 m2/g

Liquid

Particle Size Comparison Between Colloidal Silica and Silica Fume

Dp-colloidal silica: 5 nm =0.005 micron Da-silica fume aggregate: 1 micron Da,ms = Dp,cs 0.005 13 1 = 200 10 mm (with of finger) 2 meter (length of a basket player)

Va,ms Vp,cs

= = 8x10 particles x 0.5 (packing factor) =4x106 particles ( 0.005)3

Approximately 4 million individual colloidal silica particles per silica fume aggregate equals times x10
7

COMPARING Cembinder W50 vs WATER-GLASS

Silicate Water-Glass Smaller, polymer Size with different length and branching pH 10 >12 SiO2 conc. (%) 15% <35% Viscosity (cP) <10 ~180 Together with Remain as a particle Becomes monomers hydraulic binder and (Q1) water

Cembinder W50 Nanometer size, spherical particles

Cembinder Functions in Hydraulic Binders

Stabilizing - Bleed and segregation Accelerating - Set accelerator - Early strength enhancer

OPC based mortar, WCT = 0.323, Sand/Cement= 1.5

Bleeding without Cembinder

No bleeding with 0.8% Cembinder

Cembinder provides stability

Formation of CSH-gel CEMBINDER particles strengthen the network Increased surface area of the gel adsorbs water

Cement grain Colloidal silica particle C-S-H Water

Silica Concentration vs. Viscosity (Ford Cup)

60 Cembinder W36 Al EX 220 50 EX 220Al Cembinder W17 45 Cembinder W8 Viscosity (s) 40 Cembinder W8 Al 55

Larger particles

35

30

25

20

15

10 0% 5% 10% 15% Silica Concentration (%) 20% 25%

Surface modified Aluminum

Class G cement; WCT = 1.0

ACCELERATION

Calorimetric measurements Rapid Cement, WCT = 0.40

7,0 6,0 Ref 0,9 % Cemb 75 0,9% Cemb 50 0,9% Cemb 8 0,9% Cemb 17 0,9% Cemb EXP82 4,0 3,0 2,0 1,0 0,0 0 5 10 15 20 25 Ref 2

Effect (mW/g cement)

5,0

Time (h)

Cembinder calculated as dry SiO2

Calorimetric measurements Commercial cement, WCT = 0.40

3,0 Ref 0.5% Cembinder W75 0,5% Cembinder EXP 82 2,5 1,5% Cembinder W50

Effect (mW/g cement)

2,0

1,5

1,0

0,5

0,0 0 5 10 15 20 25

Time (h)

8 7

The chemistry of Cembinder interaction with Ca(OH)2

10 5 0

6 5 4 3 2 1 0 0 1 2 3 4 5 6
10 0 0

Conductivity

-5 -10

Zeta potential

Cembinder Silica fume

Reference

-15 -20 0 1 2 3 4 5 6

13,5

13

10 0

12,5

pH
10

Calcium concentration Calcium concentration

1 0 1 2 3 4 5 6

12

11,5

11 0 1 2 3 4 5 6

The suspensions were kept at 60 C and stirred continuosly for 6 hours

Work performed 1998 2001; Shondeep Sarkar & Assoc. Houston, TX

CSH-formation

Induction period

Acceleration period CSH-gel, as a membrane

CSH-gel

Work together with the Swedish Cement and Concrete Institute, 2006

Cembinder in Class G cement

Rheology (BML)
measured after 8, 30 and 60 min

w /c (class G) = 0,323 4% Cembinder

CB 88+PC CB 88+Ligno
80 60 40 20 0 0 1

CB 75+PC CB 75+Ligno

CB 50+PC CB 50+Ligno

CB 36+PC CB 36+Ligno

extrap o lated yield valu e (Pa)

Bingham plastic viscosity (Pas)

PC; dosage 0.6% bwoc Ligno; dosage 2.0% bwoc

Time (min)
200 300 400 500 600 700 800
C B8 8+ PC B7 5+ PC B5 0+ PC B3 6+ PC

C B8 8+ Li gn o Li gn C B5 0+ C B3 6+ B7 5+

Vicat setting time

o Li gn

o Li gn

final

initial

Compression Strength (M Pa)

15 10 20 25 35 30 40 45 0 5
CB 88 +P C

CB 75 +P C

CB 50 +P C

Strength without Cembinder: 30 MPa

CB 36 +P C CB 88 +L ig no +L ig CB 50 CB +L ig 36 +L ig

CB 75

no

Compression Strength 24 hours

no

no

Cembinder and Cement mechanism

From the doctorate thesis performed by Dr. Joakim Bjrnstrm, 2001 2005 for Eka Chemicals AB Methods: DSC, Diffuse Reflectance FT-IR and theoretical modeling All mixes made on pure Alite or Belite Colloidal Silica used: Cembinder 50

Cembinder Cement Mechanism

Monomeric silicates dissolved from the clinker phases are attracted by the CS The formed silicate polymer is stabilized by Calcium Hydroxide Monomeric silicate from cement grain

Calcium Hydroxide from cement grain

Cembinder particles act as nucleation sites for ions released during cement hydration.

Belite and water after 5 weeks

Belite, 1% Cembinder 8 and water after 5 weeks. The needles and the size of the grain proves the acceleration effect of CS to cement

Colloidal Silica influence on cement hydration

The relatively high solubility for Alite ensures a rapid hydration process The pore solution leaves the added nano-silica to act in saturated conditions with respect to SiO44- and Ca2+ monomers/ions

As a consequence of the high ionic strength in the pore solution nano-silica particles are not dissolved.

They are instead free to act as highly active nucleation sites for ions released from the dissolving clinker. This mechanism of action is seen to accelerate the hardening process

Effects of Colloidal Nano-Silica on the hydration of cement

Model

Colloidal nano-silica facilitates initial Alite and Belite dissolution

+2

+
-73 kJ/mol

Without nano-silica need for three water molecules.

Cembinder, Cement and Dispersant

Antagonistic Effect of PC-type Dispersants and Colloidal Silica in the Hydration of Alite Pastes

550 650 cm-1 consumption of silicate monomers 900 1050 and 1150 1300 cm-1 evolution of hydration products The Alite, SP and Colloidal silica mixtures need less than 24 hours for saturation, for the same system without SP saturation after 4 hours. For Alite and SP not saturated after 48 hours.

Antagonistic Effect of PC-type Dispersants and Colloidal Silica in the Hydration of Belite Pastes

The Belite, SP and Colloidal silica mitures need 3 weeks for saturation, for the same system without SP saturation after 24 hours. For Belite and SP not saturated after 6 weeks.

Conclusions
Nano-particles Designed particle technology True discreet particles Specifically manufactured not byproduct or agglomerates High Performance GREEN product No settling, long shelf life Low viscosity, water based

Conclusions
The colloidal silica particles act as nucleation sites Stability enhanced through CSH network formation and reinforcement Improved robustness Acceleration via increased dissolution rate of cement grains